Polyurethane of a polyisocyanate, an active hydrogen compound and a hydroxyaryl-aliphatic acid-aldehyde condensate and method of preparing same



United States Patent i" Sylvan O. Greenlee, Racine, Wis assignor to S. C. Johnson-& Son, Inc., Racine, Wis.

No-Drawi ng. Application February 21, 1957 Serial No. 641,454 a a 9 Claims. (Cl.2602.5)

This invention rela-testo novel resinous compositions of matter of the polyurethane type and is directed more a particularly to syntheticresinous compositions derived from the reaction of hydroxyaryl-aliphatic acid-aldehyde condensation products with polyis ocyanates in presence of an organic compound capable of entering into the reaction and exerting an influence upon the nature of the resulting product.

Itis known a urethane resin maybe obtained by react ing a polyisocyanateor polyisothiocyanate with a group of compounds characterized by one or more of what has been termed an active hydrogen group. Foremost among the active hydrogen compounds, at least as regards commercial development, have been the polyester compounds, although polyhydroxy-, polyamino-, polyamideand polythio-compounds are also recognized as being more or less useful in this connection. The resinous products derived from this reaction are dependent for their characteristics, for the most part, upon the structure of the active hydrogen compound with the isocyanate acting principally as a physical coupling agent between residues of the polyester or other compound. The range or variety of properties has thus been limited by the types of structures possessed by available activehydrogen com pounds, and the formulator has often found it quite difficult to develop products having the desired. characteristics.

The primary object of the present invention is the incorporation in a polyurethane-forming mixture of a compound having multiple functionality both with respect to isocyanates and isothiocyanates and active hydrogen compounds, by means of which compound a broad spectrum of polymers of this type can be obtained.

Another of the objects of this invention is to provide a new class of synthetic resinous compositions'which are capable of further reaction to give infusible, insoluble materials suitable for use as protective coatings, adhesives, andmolding resins having a variety of properties.

A further object is the synthesis along the general lines of established urethane reactions of a film-forming product characterized, by virtue of the novel reactants from which it is derived, with improved properties especially as regards resistance to attack by common chemicals, resistance to wear or damage, and resistance to penetration and solvent action by water. 7

By suitable adjustment of the conditions of the reaction and the ingredients, the product of the invention may be Patented Oct. 195a ice . 2 least five carbon atoms with a single carbon atom being substituted with two hydroxyaryl groups; and an organic compound having as activehydrogen groups at least two of the following radicals, which two maybe the same or diiferent: YH, CYYH, NH and CYNI-lg, where Y is oxygen or sulfur, which compound is free of interfering reactive groups.

It has been found that the addition of hydroxyaryl aliphatic acid-aldehyde condensates to a polyisocyanateactive hydrogen compound reaction mixture is an unusually advantageous measure for obtaining polymeric resinous compositions characterized by excellent protective coating and adhesive properties when used as a film, and high structural strength when cast into, foam resin bodies. These acid condensates are especially adapted for the reaction by virtue not only of the pres ence in each molecule thereof of a plurality of functional groups reactive with both the isocyanates and active hydrogen compounds, but because of the novel combination of hydroxyl and carboxyl radicals that make up this plurality of groups. As will be explained more fully, both hydroxyl and carboxyl radicals condense with an isocyanate group and, thus, may serve as reactive foci in the formation of a polymerrin addition, the carboxyl radical during the course of the condensation decomposes to liberate carbon'dioxide. which is of assistance in producing foam resinstructures.. Hydroxyaryl-aliphatic acidaldehyde condensates useful herein are viscous or soft resinous compositions containing one or more. residues of unique symmetrical structure and tend to contribute to the reaction product such properties as outstanding chemical resistance and superior hardness and toughness. Chemical resistance is, for example, of great value in the formulation of protective coatings which are likely to be subjected in the course of ordinary. usage to cone tact with various chemicals. The presence inzthe resin of residues having a symmetrical structure results ina more rigid product, a feature ofmuch advantage in polyurethane foams.

a The hydroxyaryl-aliphatic acidsused in the condensation may be, and preferably are, prepared by condensing a phenolic compound with a keto-acid under such conditions that two hydroxyaryl radicals are attached. to the same carbon atom of the acid. In order for the yields of this reaction to achieve useful levels, it is necessary,.first, that the keto-carbon atom occur at the position adjacent a terminal methyl group, and, second, that the ketO-acid has a least five carbons inthe aliphatic chain. The ketoacid of this type which has only four carbon atoms, aceto-' acetic acid, is highly unstable under the conditions necessary for the reaction and is unsatisfactory. The fivecarbon acid, levulinic acid, gives excellent. yields. Higher caused to assume a cellularor foam state, and accordingly, an additional aim of the invention is the provision of light-weight three-dimensional solids possessing good structural strength and, therefore, useful in load; bearing applications.

These and otherobjects are accomplished by the presacids are apparently useful, but these exist principally as laboratory curiosities and are not available in commercial quantities. There is disclosed in prior copending applications, Serial Nos. 464,607 and 489,300, filedOctober 25, 1954, and February 18, 1955, respectively, a number of illustrative acids that have been found to be particularly suitable for use, as well as methods'of; preparing the same. These acids consist of the condensation products of levulinic acid and phenol, substituted phenols, or mixtures of phenol and substituted phenolsfand shall-for the sake of brevity, be referred to herein as the Diphenolic Acid.

The terrn substituted phenols-..is usedherein to embrace phenols, and phenolic compounds wherein one or more hydrogen atoms of thephenyl nucleus is replaced by an atom orgroup that does not enter into, or otherwise interfere With, the condensation ofthe compound with the keto-acid. Thus, for example the nucleus may erably having not more than five carbon atoms, as disv 3 closed in the aforementioned application, Serial No. 489,300, or halogenated with bromine, fluorine, chlorine, or combinations thereof, provided that a total number of'substituents,including hydroxyl groups does not exceed three. The diphenolic acids derived from substituted phenols, such as the alkylated phenols, are sometimes more desirable than the products obtained from unsubstituted phenols since the alkyl groups tend to provide better organic solvent solubility, flexibility, and water-resistance, as well as influencing the nature and extent of subsequent reactions for which the acids are adapted. However, the unsubstituted product is usually more readily purified.

These hydroxyaryl-aliphatic acids react with an aldehyde, formaldehyde for example, to yield initially an alkylol condensation product. This may be illustrated by the following formula of the methylol condensation prodnot of 1 mol of 4,4 bis(4-hydroxyphenyl)pentanoic acid (formedby the addition of phenol and levulinic acid) and 2 .mols of formaldehyde:

=;m;...-oH H Home onion When phenolic compounds condense with aldehydes, the phenolic hydroxyl groups activate the aromatic nuclei at positions that are ortho and-para with respect to the hydroxyl groups. The introduction of the aldehyde into the'nuclei will, therefore, be at these positions, provided, of course, the carbon atoms there are coupled to hydrogen atoms. 4,4-bis(4-hydroxyphenyl)pentanoic acid has two. hydrogenated carbon atoms in each of its two aromatic nuclei, so that up to 4 mols of aldehyde may be reacted readily with each mol of this acid to form an alkylol condensate. In the case of alkyl and halo-derivatives'of the acid, i.e., where alkyl groups of halogen atoms have beensubstituted in the aromatic nuclei of the acid, if appreciable condensation is to take place, the substitution should not be so complete as to' remove all hydrogen atoms from the carbon atoms at the ortho and para positions. Upon the application of heat, the methylol .groups react further and yield a resinous polybasic hydroxyacid consisting of residues of: the acid linked together by methylene radicals. In those cases where the alkylol form is prepared by the introduction of aldehyde atsubstantially all the free ortho and para positions of the acid, polymerization is accompanied by the splitting off of alkylol groups and the liberation of aldehyde. A typical polymerization reaction of the material of formula I might be illustrated as follows;

onon 2H0H=oonion heat o: t a on, oniornoona h 0H g on 011 g on 'QH: CH

v c o on. omomoom oh, onionioozn Z V II I Somewhat diiferent products may be obtained by using the bis-hydroxyaryl-aliphatic acids in combination with other mononuolear, polynuclear, monohydric, or polyhydric phenols. Such materials are exemplified by phenol, the cresols, the xylenols, butylphenol, the naphthols, and bis(4-hydroxyphenyl)isopropylidene. These phenolic compounds may be partially condensed with an aldehyde, and then admixed with a partially condensed mixture of Diphenolic Acid and aldehyde to yield further valuable complex condensation products. Alternatively, these phenols may be added to the initial reaction mixture of bis-hydroxyaryl=aliphatic acid and aldehyde to yield after condensation a slightly modified product, The phenol-aldehyde condensates contain carboxyl groups in addition to alkylol .hydroxyl groups and phenolic hy-' droxyl groups. 'In the more highly condensed form, where most of the alkylol groups have been dehydrated to form methylene link-ages, the compositions contain primarily phenolic hydroxyl groups and carboxyl groups. These phenol-aldehyde condensates and their preparation are more fully described in a copending Greenlee application Serial No. 534,405, filed September 14, 1955, entitled, Phenolic Acid, Aldehyde Condensates. V

For the purpose of condensing the Diphenolic Acid, any aldehyde can be employed that will condense with the particular hydroxyaryl substituent of the acid. Formaldehyde is universally satisfactory and is preferred. It may be in the form known as formalin, a 40% aqueous solution. Formaldehyde engendering compounds, such as para-formaldehyde, trioxymethylene, and hexamethylene tetramine are also particularly suitable. The resinous Diphenolic Acid-aldehyde condensates may conveniently be used at any stage of condensation, thus providing one wishing to formulate infusible, insoluble products with a broad range of starting materials. The condensate may be the initial reaction product consisting primarily of alkylol Diphenolic Acid, i.e. an 'A- stage resin, in which case, it would be essentially a monomer containing one carboxylic acid groups, two phenolic hydroxyl-groups, and one or more alcoholic hydroxyl groups per molecule. This initial aldehyde condensate may, on the other hand, be heated to couple the Diphenolic Acid nuclei and form, as a B-stage resin, a polybasic acid containing phenolic and alcoholic hydroxyl groups. All of these condensates will have substantially two phenolic hydroxyl groups for each carboxylic acid group, since so far as it can be determined the phenolic hydroxyl groups, as such, are little involved in the linking together of Diphenolic Acid molecules during condensation. The condensation must not, of course, be allowed to proceed to a point where the product is insolu ble with the isocyanates with which it is to be reacted and certainly not to a C-stage resin that is insoluble and infusible. The extent of condensation should also be such as not to restrict the solubility of the product in solvents which might be used in applying a mixture of a Diphenolic Acid-aldehyde condensate and an isocya: nate, as in the formation of a protective coating film. The second component necessary for the reaction of the present invention is an isocyanate or isothiocyanate compound. In order that a resinous product be obtained, the isocyanate or isothiocyanate compound must contain two or more isocyanate or isothiocyanategroups, a plurality of functions being essential if a chain or cross-linked structure is to be developed by condensation with the functional groups of the condensate and/ or the active hydrogen compound. Accordingly, the iso cyanate may be defined as a compound having the general formula R(NCX),,, where X is a chalcogen having an atomic weight less than 33, i.e., oxygen or sulfur; z is an integer of more than one; and R is a polyvalent organic radical with the number of yalences being equal to z. There are numerous compounds coming within this formula that are suitable for the reaction and ;no attempt will be made to give an exhaustive, list. The following are considered illustrative and will suggest to the expert a variety of others; alkylene diisocyanates; such as ethylene diisocyanate, ,trimethylene diisocyanate,

qtetramethylene :diisocyanate, hexamethylene diisocyanate,

adecamethylene diisocyanate, and their corresponding sulz-fur analogues;cyclo-alkylene diisocyanate, such as cyclo- -;pentylene diisocyanate, cyclohexylene diisocyanate, and their corresponding sulfur analogues; aromatic diisoacyanates, such as m-phenylene diisocyanate, naphthalene diisocyanate, diphenyl-4, 4-diisocyanate, and their corresponding sulfur analogues; aliphatic-aromatic diisocyvanates, such. as ixylene-1,4-diisocyanate, .diphenylene methane diisocyanate and their corresponding sulfur wanalogues; hetero-d'iisoand diisothiocyanates, such as SCNCH OCH NCS and SCNCI-I SCH NCS; and isocyanates ad isothiocyanates having more than two isocyanatelor isothiocyanatesgroups, such as benzene 1,2,4-triii'socyanate, l,2,2 triisocyanatobutane, and toluene triisocyanate. From among these and other polyisocyanates and :polyisothiocyanates, the :following are preferred largely by reason of their ready commercial availability: toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, methylene bis-(4phenyl isocyanate), 3,3 bitolylene 4,4 diisocyanate, and hexamethylene diisocyanate. In order to simplify the remainder of the discussion, the repetitious recital of both the oxygen and sulfur forms will be dispensed with; only the oxygen compound will be given but will be understood as embracing the corresponding sulfur analogue.

While, as has already been mentioned, urethane reaction requires a polyisocyanate compound, it.is desirable for certain applications to. alter the product by using, in addition, a minor portion of a monoisocyanate. of the reactionproducts of diphenolic acids with polyisocyanates tend to be brittle infusible products; on the other "hand, this tendency may be frequently counteracted by the addition tothe reaction mixture of a proper amount and type-of monoisocyanate,- particularly when combined with the:proper amount and type of ac-tive hydrogen compound. Examples ofsuitable monoisocyanates are octadecylisocyanate and hexyl isocyanate, to mention just a few "of the simpler compounds. Long-chain monoisocyanates, i;e., having more than 11 carbon atoms, are more effective as regards flexibility; Unsaturated compounds can also be utilized and provide an additional curing or converting aid. The amount of the monocompound that is added to the reaction mixture will vary depending upon the characteristics desired in the product. 'As a general rule, there should be present a greater amount ofthe poly-compound than the mono-compound, which is to say, thatthe monoisocyanate should be less than 50% of the totalof all isocyanates, in the reaction mixture. If a. more rigid, brittle material is sought, the quantity of the mono-form should be decreased while, if more flexibility is the desideratum, it should be increased toward the upper limit just mentioned. The functional group of the mono-form may react with the carboxyl or phenolic hydroxyl groups of the acid to reduce cross-linking between adjacent molecules of the polymer and thereby enhance the softness and pliability of the polymer in proportion to the amount present, or a functional group of one or more molecules of the monoisocyanate may react with the methylol groups of the "condensateja'nd, thus, preclude further growth of the chain. Reaction of the. mono-compound and the active hydrogen compound is also a possibility, which reaction may alsoend the growth of the polymer molecule or reduce cross-linking.

The active hydrogen compound is the final component of theireactionmixture described herein. For the pur- :pose of the invention, the active hydrogen compound must satisfy two requirements: First, it must include at least twoofythe radicals --'OH, COOH, -CONH [*NHQ, 'SI -I, -'COSH, .CSOH, (3581-1 and CSNH rwhichtwo may be the same or. different radicals; and,

; second, it must be free of interfering reactive groups. To simplify the-discussion, compounds meeting these Some.

6 requirements have been grouped into the following classes: (A) the,polyhydroxycompounds, (B) the polybasic acids, (C) the polyamines and polyamides, (D)

miscellaneous analogous sulfur compounds, and (E) the polyester resins. As will 'be seen later, compounds containing more than one type of radical, i.e., hybrid compounds, have not been classified independently but are included in these five groups. In this case, as' a rule,

the compound is classified in that group, .of the several t glycol; polyalkylene glycols, such as diethylene glycol and the Carbowax. series manufactured and sold by i the. Carbide and Carbon .Chemical Company; :glycerol,

erythritcils, higher alcohols, such as mannitol and'sorbitol; aromatic alcohols, such as resorcinol, hydroquinone, and bis-phenol; and resinousalcohols, such as the epoxides. Mixtures of the Diphenolic Aci'd with dihydric phenols,

particularlythe alkylidene diphenols, in reaction with'the' isocyanates give rigid, :infusible products possessing excellent chemical resistance -to alkali and water when formed as films and-outstanding rigidity when cast as foam resin structures. It is well known that the polyhydric alcohols, such as the long-chain glycolsygive on reaction with the isocyanates soft flexible-type compositions of relatively low chemical resistance. "Modification ofthese compositions with Diphenolic Acid-aldehyde condensateshasbeen found to greatly increase the chemical resistance ofprotective coatingfilms prepared therefrom as well as to strikingly heighten the rigidity of foam resin structures produced therefrom.

Next in the classification are the polybasic acids. Examples of these acids are the saturated aliphatic polycarboxylic acids such as adipic acid, 'tricarballylic acid and azelaic acid; unsaturated aliphatic polycarboxylic 'acids, such as fumaric acid and aconitic acid, and aromatic polybasic acids, such as the isomers of benzene dicarboxylic acid. Polyfunctional acids are of particular interest in connection with the formation of resin foams as the carboxyl group decomposes upon reaction with an isocyanate to release carbon dioxide. Withthe addition of a Diphenolic Acid condensate, further carbon dioxide is available from the carboxyl group of the condensate and enhanced foaming results. This is advantageous since enhanced foaming was previously obtained by adding substantial amounts of water. As. is well known, water reacts with an isocyanate to yield carbon dioxide and a carbamide. In addition, the acidcondensate serves to strengthen the rigidity of the foam and causes the cell arrangement to be disconnected or closed rather than open. Where the combination of isocyanate, polybasic acid and condensate is used-as a film or-coating, thelast presumably due to the hydrophilic character of such acids. Films which are highly hydrophobic are whitened by, prolonged contact with water. By adding material having hydrophilic properties to the film-forming mix- .ture, the hydrophobiccharacterof theifilm can be reduced 'sorbital, mannitol, glycerine,

undue loss of overall resistance to water.

The thirdclass, the polyamines and polyamides, is characterized by the presence of an NI-I radical, which in the case of the polyamides is combined with a carbonyl group as the radical CONH Examples of this class are the alkylene and polyalkylene diamines, such as ethylene diamine and hexamethylene diamine; heterocyclic polyamines, such as diethylene 'diamine and triethylene diamine; and aromatic polyamines, such as phenylene diamine; the alkane diamides, such as malonamide, succinamide and adipamide; aromatic diamides, such as phthaldiamide; and the resinous polyamides. 1 Compounds containing at least two amino radicals are of particular value in accelerating the reaction. It is interesting to" observe that polyamines are inclined to impart flexibility to products while polyamides are disposed to impart rigidity. Thus, a product of balanced flexibilityrigidity, or increased rigidity, may be obtained by the addition of a Diphenolic Acid condensate. The polynitrogen compounds are also useful where products having high chemical and water resistance are sought.

Another class of active hydrogen compounds is the sulfur-containing chemicals. As a general rule, this class embraces. the corresponding sulfur analogues of the members of the other classes. Thus, polythiols, such as ethanedithiol and propane-trithiol, polythioacids, polythioamides, .and resinous polythio-compounds are included, among others. The most useful of these compounds for this invention are the thioresins sold under the trade name Thiokol and prepared by reacting an alkaline polysulfide with an organic dihalide, trihalide, or mixtures ofthe two. These polymers are thought to have thiol terminal groups. Preferably, the liquid polymers are employed because of their relatively low molecularvweight, ease in handling, and ease in admixing with other reactants. As is well known, these materials undergo reaction with various coupling agents or can be cured with numerous curing agents to form rubbery polymers which are usually soft and flexible. When compounded with a Diphenolic Acid condensate and an isocyanate, thio-resins yield smooth, tough, flexible products having much augmented chemical resistance. Other sulfur compounds, such as the simple mercapto acids and mono and dimercaptans, may be used in conjunction with these condensates in the formulation of valuable coating, adhesive, and molded objects.

Finally, there are the polyester resins, which are polymers, having recurring ester linkages and unreacted hydroxyl and carboxyl terminal groups, formed by reacting a polybasic acid'with a polyhydric alcohol. The nature of the reactive groups is determined by the proportion of the reactants. Thus, an excess of the alcohol favors terminal hydroxyl groups while an excess of acid favors terminal carboxyl groups. By properly balancing the amounts of each, terminal groups of both kinds can be procured. There are a number of polyester compounds available commercially, one example being a series having hydroxyl values ranging from 70l000 and acid numbers ranging from 0-80 sold under the trade name Multron by the Mobay Chemical Company.

Among the polybasic acids that can be used are succinic, adipic, maleic, sebacic, azelaic, fumaric, and dimerized acids, such as dimer fatty acids prepared and sold by Emery Industries, Inc. Suitable polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, dipentaerythritol, tripentaerythritol, trimethanol propane and triethanol" propane.

It is well known thatreaction of polyester resins with the polyisocyanates results in soft flexible foam resin structures and soft coating compositions and molding- 1 materials. The use of Diphenolic Acid-aldehyde condensates in conjunction .with these polyesters and isocyanates has been found to be an excellent modeof promoting rigidity in foam resin structures of this type. Thus,

' moderately to completely stiff three-dimensional articles can be easily obtained merely by incorporation ofthe condensate in selectively increasedamounts. Variation in density of the solid product may also be effected by this means. In the field of protective coatings and adhesives, an analogous hardening and toughening influence by the Diphenolic Acid condensate exists so that products of this kind display substantially enhanced resistance (1) Hydroxyl group:

ROH+RNCO- R'NHCCOR (2) Carboxyl group: RCOOH+RNCO EI-INHCOOCOR RNHCOR I-CO 3) Primary amino group:

RNH +RNCQ- RNHCONHR (4) Amide group:

' ROONH +RNCO- R'NHCONHCOR- The same reactions take place where sulfur is substituted for any oxygen in these reactants.

In the present invention, it is postulated that the reaction occurs within a system of three .or more components, each of which is characterized by at least vdouble functionality. Accordingly, while the union of any two groups will proceed as set forth above, it will be appreciated that the resultant product will in any case be polymeric. Further, it will beapparent that the-possible arrangements that may be taken within the polymer .molecule by the residues of the reactants are entirely too numerous to be illustrated herein. Due to the high reactivity of isocyanate' groups, one would expect the condensation between these groups and the functional groups of the Diphenolic Acid condensate to take precedence over any possible reaction between the condensate and the active hydrogen compound. Thus, it can be predicted that the polymer molecule comprises residues of the condensate linked together by isocyanate residues alone or which are themselves coupled by means of the residues of the active hydrogen compound. Where, the isocyanate and active hydrogen compound are difunctional, the condensate residues would be separated by essentially linear chains with cross-linking taking place between the residues in adjacent chains due to the excess functionality of the Diphenolic Acid condensates. With isocyanates and/or active hydrogen compounds having more than two functions, cross-linking to a much greater degree would ensue. I

The diversity of the isocyanates and activehydrogen compounds that can be employed makes it virtually impossible to prescribe a fixed set of rules governing the choice of a class of compounds, the particular member of that class, as well as the amounts. of the member. Some of the classes and their individual members are more or less equally suited for use in producing a given product so that a choice depends in many instances upon the personal preference of the formulator, such preference being based, for example, on his greater experience in working with certain types of'materials than with others. As a rule, aliphatic compounds favor flexibility and softness with the extent of these properties increasing with the chain length.- Conversely, compounds having necessary at room temperature.

. 9 ertiesvcan be developed by the careful selection of reactants: that is, all :may promote flexibility, all may promote rigidity, or some one and some the other in order to cover the gamut between the two extremes.

Along with the specific reactants, the properties of the product "are also influenced by the amount of each reactant that is employed. Because of the high reactivity of the isocyanate, for the purpose of defining proportions may be considered that the Diphenolic Acid-aldehyde condensate andactive hydrogen compound react as a unit with the,-isocyanate Within this suppositious unit, the activeyihydrogen compound may constitute from about to about "65 ofthe' whole, determined on the basis of equivalent'weight, with thefcondensate making up the rest. Below*5%, the effectsofthe active.

hydrogen compound are rarely significant, while above 65%, the contribution of the condensate is counteracted excessively or is jfnot sufficiently great to be :of real value. Experience has indicated that the Diphenolic Apid condensate and active hydrogencompound, considered to-* tion usually prevails where all of the functional groups of condensate and active hydrogen compound are reacted with functional groups. of the .polyisocyanate. For this reason, a preferred rangeis 2: 1' to 1:2 015 condensate and active hydrogen compound to isocyanate onan equivalent basis with a 1:1 ratio beingtmost desired.

If a 1monoisocyanate"is employed along with the polyisocyanate, the number] ofreactive rfoci of the Diphenolic Acid condensate and active hydrogen compound available to the functional ,groups of the polyisocyanate is lessened. In arrivingat the amounts of reactants to be utilized, the mono-compound must therefore be considered, and in such case the equivalent weight of the isocyanate is the total of the equivalent weights of the monoand poly-compounds.

In general, the procedure by which protective coating films or molding compositions are prepared in accordance with the present invention involves merely adding cyanate, .admixingand converting the mixture by exposure either to. normal temperatures or to heat. In some cases, it is desirable to dilute some or all of the reactants, e.g., in order to lowerthe viscosity of the mixture and, thus, vary the film thickness of a single coat, and/or in order to d issolve the condensate, where Any solvent that is inert to both the condensate and isocyanate may be-used, an example being methyl ethyl *ketone among many others.

- The mixture of reactants, either diluted or not, has been i found to be reasonably stable .formoderate periods at normal ttemperatures. "Such .stabilitytisa tfeatureof some importance as it'permits large quantities of the mixture to be made upfat one time and then used as needed.

For heat -cure,jtemperatures ;of about;85.-225 C. for times of about one hour =10. about five :minutes have been found satisfactory. For a normal temperature cure, it .is preferred that any of the well known conversion catalysts for -reactionsof type, such as .triethanolamine, be added in small amountswin order to, reduce. the amount ,of .timelnee ded for the film to harden. When early c'on version .is of no special advantage, the catalyst maybe expected. As awhole, however, the;fil ms possess char- :acteristics@that-comparepfavorably with many other availsolution for more than 50 hoursg-without any indication of failure. r

Where .solid foam or cellular structures .are desired, they may be obtained by mixing we-concentrated vDi- -phenolicAcid condensate and active hydrogen compound with a suitableconversion catalyst, of which triethanol- -amine is again .can example, in an appropriate reaction vessehat temperatures at or above the melting point of the "condensate, whereit is solid atroorn temperature,

adding the isocyanate while agitating, pouring the mixture into a mold, allowing the mixture to foam unim- ."pededyand convertingby' heating,as in a draft oven, at a temperature of'about 85-15050. or more for from about 530minu'tes, or bynorm al temperatures-for much longer periods. .Although notiessential, .it isusually desirable .xto .employanemulsifier in order to obtain a more homo 'geneous mixture of thereactants. The. reaction usually proceeds instantaneously at these temperatures. The .in-

stant process -may be carried out; readily in. any system which :provides for stirring and has sufficient space :for

.the foaming action to proceed unhindered. .A 1modification of .a nnit :currently used in commercial urethane @foameproduction maybe employed. Such a system comprises'two supply tanks connected to a pressure-mixing nozzle by suitable feed lines. One tank :contains the iso- "cyanate and the other tank, which may have to .be heated,

contains .the .Diphenolic Acid condensate and active hydrogen .compounduemulsified with the emulsifying agent and catalyst. The condensate and isocyanate areded from thetanks. tothe nozzle where they are mixed under pressure and flowed into pans where the foaming reaction is allowed to proceedunhindered. Again, the foams may be cured in a'suitable draft oven at elevated temperatures, thus accelerating the operation. Although the foams may be cured by exposure to normal temperatures as in the case of the films, this considerably prolongs the curing time and a heat cure is preferred.

As has already been briefly mentioned, the Diphenolic Acid condensate as well as carboxyl-containing active hydrogen compounds are especially well suited for the formation of urethane foams by reason of the carboxyl group or groups which they contain. These groups in the course of the reactiondecompose to form gaseous carbon dioxide which bubbles through the mixture to produce a cellular structure. Thus, a foaming medium is inherently present, eliminating the-need, in many instances, of an external foaming agent, this being especially true where a polybasic acid constitutes the active hydrogen compound. With other active hydrogen compounds, it occasionally proves advantageous to add small amounts of water, say up to about 5% by weight of the mixture,

. to assist in the foaming action. The useof water merely as an assistant does not add unduly to the curing time of one hour or lesstwhioh isflin distinct contrast to typical present commercial polyurethane foam processes, wherein water is relied uponcas-the sole or principal foaming agent, which require .apost-cure of some 24 hours duration. The density .of-the .foams made as: described herein varies not only with the particular isocyanate selected for reaction but with the temperature of the conversion as well. It has been found that as the temperature of this stage is increased, thedensity of the foam also increases, due presumably to therincreased loss of CQgfrom the mixture at the higher temperatures.

The toughness and rigidity Jcontributed bythe Diphenolic Acid-aldehyde condensates are especially significant in the ;case of foam structuressince such structures made inlthe past from isocyanate and active hypart, been. of rather soft, spongy texture; The. toughness and rigidity-together with-the resistance. to .water *and'common chemicals that the present foams exhibit as'well asa very low density when compounded to' this 'end, constitute a rather exceptional combination in this "structural components alone or in conjunction with outer coverings of-wood'or metal;

For the'sake of brevity as well as convenience, most of the remainder of this disclosure-will be presented in the form of four tables, 'the first three giving examples 'otthe three reaction components, along with some pertinent information concerning .them, andi-the fourth providing working examples of the invention in. the coating field. I l r i The acid condensates mentioned in Table I were all prepared in accordance with the following procedure; A mixture of 3 mols of the specified'monohydric phenol, 1 mol of levulinic acid, and 250 parts of 37%.aqueous "hydrochloric acid was agitated at 50 C. for'72 hours.

'. The upper organic layer-was removed from the aqueous HCl by decantation. The product was then subjected to vacuum distillation, using a water aspirator, at a pressure of 15 to 30 mm. with the application of heat 'until the temperature had reached 165-170 0., thereby removing volatile materials including any unreacted HCl, water, and major portion of unreacted phenol andsome of the unreacted levulinic acid. Vacuum distillation was continued using a vacuumpump system which reduced the pressuredown to 1 mm. of mercury, while the reacminutes.

Acid-aldehyde condensate H Isocyanate equivalent served) Abhre- Condensate viat on Condensation of alkyl 'diphenolic acid an formaldehyde with alkaline catalyst: A I mixture of 314 parts of the Diphenolio 1 Acid obtained from ortho-cresol and levu- ,linic acid and having an acid value of 139 and a saponification value of 192, 172 parts of formalin (38% aqueous formaldehyde), and 15 parts of sodium hydroxide as a aqueous solution wasplaced in a 3-necked reaction flask provided with a mechanical stirrer, a reflux condenser; and a thermometer. With continuous agitation the temperature was gradually raised to 100 C. and held at this temperature for 1 hour and 20' minutes. The water was then removed by vacuum distillation at a pressure of 20-30 mm. using a water aspirator pump, the charge being heated to 96 0 during the distillation. The residual aldehyde condensate amounted to 360 parts. Condensation of DPA l and formaldehyde with alkaline catalyst: A mixture of 286 parts of Diphenolic Acid from 3 mols of phenol and 1 mol of levulinic acid, having an acid value of .141 and a saponificatio'n 7 value of 201, 258 parts of formalin, and "parts of 10% aqueous sodium hydroxidewas heated with continuous agitation as in No. 1 at a temperature of 100. C. for 1 hour.

The water was removed by vacuum distillation at a pressure of -30 min. with the't'emperature' rising to 92 C. during the final distillation. The residual aldehyde condensate amount to 352 parts.

Condensation of excess DAP and formalde- 1 hyde: A mixture of 626 parts of the D1- phenolic Acid obtained trom- 3 mols of phenol and 1 mol of levulinic acid, hav ng an acid value of 153 and a sapomfication value of 204, and 350 parts of formalin was heated at 100 C. with continuous agitation for a period of 1. hounand' minutes. The water was removed by distillationat, a pressure of 2030 mm. using an aspirator' pump. The residual aldehyde condensate.

amountedto 732 part s. r

1"; AOL... 52.6

a.-- AC3. its. 2

12 Tqbl'I..Re'presentative Dipheno lic'Acid-aldehyde I condensate-Continued 1 Condensate I Condensation of DPA, bis-phenol and formaldehyde with acid catalyst: A mixture of 429 parts of a'Diphenolic Acid obtained from 3 mols of phenol and 1 mol levulinic acid, having an acid value of 152 and a saponification value of 208,.342 parts of bis(4-hydroxyphenyl)dimethyl methane,

480 parts of formalin, and 1.92 parts of oxalic acid was heated'at 100 C. for a.

period of 1 hour and 10 minutes, with con 'tmuous agitation. The water layer ,was v removed by decantation and the organic r-- s resin layer washed 3 times with hot water. The orgamc resin layer was then tread Y from the last traces of water by. vacuum distillation at a pressure of 20-30 min, i using a water aspirator pump, and a temr peratureof 84C. The resulting product amounted to 912 parts.

Condensation of alkyl dipheiiolic acid and formaldehyde withacid catalyst: A miirture of 1 57 parts of the Diphenolic, Acid used in N 0.1, 86 parts of formalin and 0.35 part of oxalic acid was heated with continuous agitation at 100 C. for l hour. The water layer was removed 'by' decantation and the phenolic resin layer washed 3 times with hot water. The resi du a1 r esm layer was dried by vacuum distillation at a pressure of; 20 30 mmL, using a watenaspirator pump, with the temperature using to 100 C. The product amounted to 176 parts.

Condensation of alkyl diphenolic acid and formaldehyde with acid catalyst: A mixture of 157 parts of a Diphenolic Acid 0btamed by the reaction of 3 mols of meta cresol with levulinic acid, having an acid value of 165, 86 parts offormalin, and 0.35 part of oxalie'acid was heated at 100 C. with continuous agitation for a period of lhour The water layer was removed. by decantation and the phenolic resin layer washed- 3 times with hot water.. The residual resin layer was finally dried by vacuum distillation at a pressure of 20i i0gmm., using a water aspirator pump. while heating to 93 C. The .product amounted to 164 parts.

1 D PA is a trademark for 4,4-bis(4 hydroxyphenyl)pentanoie acid.

7 It willbe observeclthat an isocyanate' equivalent-is specified for each'acid. The is'ocyaiiate equivalent is de- 5 V fined as'thjweight of the acid which will react with one equivalent of the isocyanate and'will be of assistanccin selecting actual amountsof the acid that should beused.

' The method used in determining the observed'values as listedinvolves reacting a sample of the acid with an excess of toluene-2,4-diis'ocyanate enamels determining the exces s isocyanate by reaction with di-ii-butylamine. I Specifically, the technique used is as follows amount equal'to 1% of the total weight of isocyanate and the acid. The mixture is refluxed for a-period of one 3 hour. After coolingto room temperature, the condenser wallsai'e rinsed with about 25 ml of ifedistilled toluene. To this nixture is added 25 of 2N di-n butylamirie.

'This' mi it ui e is 1 warmed up; to the boiling point} allowed tofstandforfjone hour at which point ml. of riiethanol i'sfadded' and the excessdifii-butylaminefbacli itratd .with 1N alcoholic hydrochloric acid. By carrying out .t ,efpi' eparatiou of the" acids with great care valuies atbr nem a t e te e l ee e m heac d mb r en ie l e aeid 1 st t 12,907,719 p p 14 meaning, which is the number of milligrams or potasof 1 gram of the sample, and provides an indication of .sium (hydroxide necessary to 1 neutralize the acid content .the degree of acidity of the product.

Table II.-Representative isocyanates Amine equivalent Commercial source, trade name, and abbreviation Structure I Observed Theory i E. I. duPont de Nemours & 00., Inc. NCO 90.62 87:01

I NCO To1uene-2,4-diisocyanate H E. I. du Pont de Nemours & 00., 1110.; Hylene M; Hy OCN(|JNC 0 139.98 125.12 p i H Methylene bis(4-pheny1 isoeyanate) National Aniline Dim; Nacconate 200; N 200 o 0NNo 0 132.78 132. 13

3,3'-bito1y1ene-4,4-diisocyanate III C O Mobay Chemical 00.; Mondur N5; M0 N5...; 116.58 105. 09

Naphthyleue-l,5-diisoeyenate Mobay Chemical 00.; Mondur TM; MO TM-.. CH C-H 107. 78 123. 45

Tritolylmethane triisocyanate Mobay Chemical Co.; Mondur HX; M0 HX OCN(CHz)eNCO 103. 39 84. 01

Hexamethyleue diisocyanate i Approx. {Mobay Chemical 00.; Mondur 1?; MO I NC 0 119 119 Phenyl isoeyanate Approx. Mobay Chemical Co.; Mondur NP; MONP 169 169 Naphthyl isoeyanate Shell Development 00.; Durnedis'soeyanaltej Dur 0 CN NO 0 111. 22 108. 12

CH; CH;

2,3,5, 6-tetramethyl-lA-benezene diisocyanete scrved values' were obtained for use as a guide in formulating reaction products therefrom as these values provide a measure of the actual purity of each compound. The analytical procedure used to determine amine equivalents of diisocyanates is found in Monsanto Chem- -mercially are not necessarily chemically pure, the obical Companys Technical Bulletin #P-IZS and is generally as follows:

Twenty-five milliliters of redistilled toluene and 25' ml. of approximately 2 N di-n-butylamine were placed in a carefully cleaned and dried 250 -ml. or 500 ml: Erlenmeyer flask. The sample of diisocyanate drawn into a warmed glass bulb and the neck sealed ofl in a flame. Sample weight is determined by the difierence in Weight between the empty and the filled bulb. The bulb was immersed in the Erlenmeyer flask and crushed beneath the surface of the liquid. The solution was heated to boiling and allowed to cool 1 hour; 100 ml. of technical methanol and 0.5 ml. of bromophenol blue indicator was added. It was then titrated with 1N HCl to a yellow end point. The indicator was prepared by taking 0.1 g. of .bromophenol blue, 1.5 ml. 0f.0.1.N NaOH diluted with 100 ml. of distilled H O. The average precision demonstrated by these determinations was :L-1.29%.

Table IIL-Active hydrogen compounds A. POLYHYDROXY COMPOUNDS Abbrev. Isocyanate equivalent Compound used in tables Observed Theoretical Ethylene glyml 27. 64 31.03 1,4-bu 39. 26 45. 06 1 Diethylene glyc 44. 76 51.16 Polyethylene glycol'400. I 163. 48 190-210 (Carbide & Carbon Chemicals 00., described as having M.W. 380-420; viscosity 7.3 centistokes at 210 F.) Polyethylene glycol 1000. 409. 76 500 (Carbide & Carbon Chemicals 00., M.W. 950-1,050: viscosity 17.4 centistokes at 210 F.) Polyethylene glycol 4000. PG 4000-- 1,851. 9 1, 500-1, 850 (Carbide & Carbon Chemicals 00., M.W. 3,000-3,700; viscosity 75-78 centistokes at 210 F.) Polyethylene glycol 6000. PG 6000-- 3, 475. 6 3, 000-3, 750

Carbide & Carbon Chemicals Co., M.W. 6,000-7,500; viscosity 700-900 centistokes at 210 F.)

lycerol (0.1. grade) G. 29. 53 30. 67 Pentaeryth PN..---.- 24. 24 34. 04 E%on 864 Epon 864.. 311. 63 (S ell Chemical Corp. An epoxy resin prepared from the condensation of epichlorohydrin with bis(4-hydroxyphenyl)-dimethyl methane in the presence of alkali having a melting oint (Durrans Mercury Method, Journal of Oil & Colour Chemists Assoc. 12, 173-175 1929]) of 40-45 C.; epoxide equivalent 800-375.) E on 1007 Epon 1007- 360. 29 (S ell Chemical Corp. An epoxy resin prepared from the condensation of epichlorohydrin with bis(4-hydroxyphenyl)-dimethyl methane in the presence of alkali having a melting point (Durrans Mercury Method) of 127133 C.; epoxide equivalent 1,550-2,000.) Bis(4-hydroxyphenyl) -dimethyl methane-formaldehyde condensate. BDF..-.'-. 98. 78 (In a 3 liter, 3-neck flask provided with a mechanical agitator, a thermometer, and a reflux condenser Was placed 912 parts of bis(4-hydroxyphenyD-dimethyl methane, 960 parts of 37% aqueous formaldehyde and 2.3 parts oxalic acid. With continuous agitation the reaction mixture was heated to reflux temperature and refluxing continued for 1 hr. After permitting the reaction mixture to cool to around 50- C. the water layer was removed by decantation. The phenol-formaldehyde layer Wasthen Washed 8 times with water which in each case was removed by decantation. The last portion of water was removed by distillation at reduced pressure using a water aspirator system which gave pressure around 30-40 mm. The flask temp. during the removal of this last portion of water ranged from 70-90 C. The product, amounting to 1,065 parts, was a clear, heavy, syrupy material. The non-volatile content was 83.4%.) p-t-Butylphenol-formaldehyde condensate. BPF 156. 54 (The procedure of preparation, including the dehydration step, was the same as that used with bis(4-hydroxyp enyl)-dimcthyl methane above. A mixture of 1,000 parts of paratertiary butylphenol, 1,067 parts of 37% aqueous formaldehyde, and 10 parts of sodium hydroxide was used to give a final yield of 1,470 parts of a clear, almost colorless syrupy product. The nonvolatile content was 93.6%.) Resorcinol. .105. 38 55. 05 Hydroquinone, C. P H 161. 44 55. 05 1,5-dil1ydl0Xy anhthalene D N 217. 38 30. 08 4,4-dihyd.roxybenzonhennne DHB 221. 0 107. 1 Bis(4-hydroxyphenyl)-dimethyl methane BDM 304. 22 114. 0

POLYBASIC ACIDS Azelaic acid Az- 87. 53 94. 11 Adipic acid.. AA 71. 35 73.07 Aconitic acid AcA 57. 28 58.03 Fumaric acid. FA 52. 36 58. 03 Diglycollc acid DGA-..-- 166. 02 67. 04 Isophthalic aci d 485. 29 83. 06

1 Preparation of these epoxide 1113126118618 as well as illustrative examples are described in 11.8. Patents 2,456,408, 2,503,726, 2,615,007,

. 2,615,008, 2,688,805, 2,688,807, and 2,698,31

2,907,719 17 18 Table [IL-Active hydrogen compoundPContinucd o. IEOLYAMINES AND POLYAMIDES Abbrev Isocyanate equivalent Compound used in tables Observed Theoretical Hexamethylenedi 1min a 31. 96 29. Diethylenetri amine 17. 99 20. 63 Triethylene tetraarnine 27. 26. 38 Phenylene diamine 41. 54 27. 03 Diethannlamine 41. 2 35. 05 Arlipamidn 106. 22 38. 04 Phthtunmidp 14.0.36 41. 04 Malonamide 63. 25. 52 p-Toluenesulfonamide- 98. 63 85. 60 Polyarnide resin. 380. 03 312. 03

(In a 3 liter, 3-neck flask provided with mechanical agitator, thermometer, and water trap with a reflux condenser above was placed 1,545 parts of Emery Industries, Inc, Dimer Acid #955 (a dimerized soya bean oil acid) and 269 parts of ethylenediarnine. The ii ask was provided with an inlet for an inert gas. With continuous agitation and in an inert atmosphere of nitrogen gas the reaction mixture was heated from 94220 C. over a period of 12 hours. 165 parts of water were removed from the reaction mixture during this period. The resulting polyamide resin had an acid number of 3.2, and a softening point of 87-89 C (Durrans Mercury Method) i i D. SULFUR-CONTAINING COMPOUNDS Thiomallc acid Thioglycolic Mid E. POLYESTER RESINS PER 1---- 246.1

PER 2-.-. 107. 4

PER 3---- 929.0

. PER, 4...- 480. 5

PER 5 1,046

2 In a 3-neck flask provided with a thermometer, a condenser attached through a water trap, and a mechanical stirrer was placed 502 parts succinic anhydride, 943 parts azelaic acid, and 414 parts ethylene glycol. The reaction mixture was gradually heated to 204 C. with continuous agitation at which point a sufficient amount of xylene was added to give constant refluxing at 195204 C. After refluxing for 2 hours at 195-204 C., 462 parts of glycerol was added dropwise over a period of 1 hour and 10 minutes. Refluxing was continued for 2 hours and 15 minutes at 204220 C. at which point most of the xylene was removed by distillation. The viscous syrupy product had a non-volatile content of 96.5% and an acid value of 6.

3 As in the preparation of PER 1, 925 parts of glycerol, 785 parts azelaio acid, and 418 parts of succinic anhydride were refluxed with xylene at 184-204 C. for 3% hours. Most of the xylene was removed by distillation at 200205 C. The viscous syrupy product had a non-volatile content of 95% and acid value of 7.6.

4 As in the preparation of PER 1, 212 parts of diethylene glycol, 292 parts of adiplc acid, and 2 parts of glycerol were refluxed with xylene at 200-225 C. for 6 hours. The xylene was removed by heating at 220225 C. with reduced pressure of around mm. The viscous syrupy product had an acid value of 12.8.

5 As in the preparation of PER 1, 212 parts of diethylene glycol and 292 parts of adipic acid were refluxed with xylene at 200 225 C. for 6 hours. The xylene was removed by heating at 200-225 C. with reduced pressure of around 70-80 mm. The viscous syrupy product had an acid value of 87. 7

As in the preparation of PER i, 212 parts diethylene glycol and 355 parts of ghthalic anhydride were refluxed with xylene at 200-225 C. for 6 hours. The xylene was removed by heating at 220-225 C. wit reduced pressure of around 70-80 mm. The viscous syrupy product had an acid value of 60.

The following examples, presented in tabular form to. conserve space, illustrate the conversion of mixtures of Diphenolic Acid and polyisocyanatcs alone and modified with a monoisocyanatc to insoluble, infusiblc products. Each of the acid condensates was dissolved in the designated solvent in the indicated amounts to a nonvolatile content of 40-60%. The isocyanatcs and active hydrogen compounds were used inmost examples at non-volatile content. In some instances, however, the active hydrogen compound was dissolved in small amounts of the same solvent for solubility purposes be- 75 formulated accordingly to obtain the desired character forebeing added to the solution of the acid condensate.

, The mixtures obtained by adding all the ingredients to- Table lV.Examples of the znventzon as a coatmgCont1nued D. SULFUR-CONTAINING COMPOUNDS Conversion Withstood in hrs. Trleth- Ex. No. Acid con- Parts Isocyanate Parts Active Parts ylaminc Solvent densate 3 compound catalyst, Time Temp 1110 at 5% aq. parts (hrs) 0. 100 0. r N aOII at C E. POLYESTER RESINS Parts Conversion Withstood in his.

. O y.- Ex. No. Acid con- Isocyanate Parts Active Parts amine Solvent densate Uncompound cata- Time Temp, 1120 at 5% aq. Fused 5 fused lyst, (hrs) O. 100 C. NaOI-I parts at 25 0 PER 1.-.. 0.5 175 13 0. 08+ PER 5-.-- 0.5 175 17- .25 PER 4-.-. 0.5 175 17 .25 PER 5.... 0.5 175 17- 7. 5 PER 2.--- 0.5 175 17-- 9 PER 1.-.- 0.5 175 17-- 80+ PER 1--.- O. 5 175 17- .08-I- PER 1-... 0. 5 175 17- 1 PER 3--.- MEK/MIK... 0. 5 175 17 2 PER 1--.- ME 0. 5 175 5 .25 PER 3.... MIX... 0. 5 175 5 .25 PER 3.... MlK/MEK... 0. 5 175 17- 2 PER 4.... MIK/MEK... 0.5 175 17-- .5 PER 5.-.. MIK/MEK..- 0.5 175 17 7. 5 PER 3.-.. MIK/MEK..- 0.5 175 17- 1 PER 2.-.- MIK/MEK-.. 0.5 175 17-- 7. 5 PER MIX/ME 0.5 175 10 .08 PER MIK/MEK... 0.5 175 17- 2 PER 4.-.- MIK/MEK-.. 0.5 175 17-- 80 PER 5.-.- Dio ME 0.5 175 17 2 PER 1...- MIK/MEK... 0.5 175 17-- 80 PER 1..-- MEX/Benz.-. 0.5 175 17- 2 PER 1.... MIX 0.5 175 17- 80+ PER 1.... MIK/MEK... 0.5 175 17-- .16 PER MIK/MEK... 0.5 175 17 5 PER 1.... MIK/MEK... 0.5 175 17- 80+ PER 1-..- MIK/MEK-.- 0.5 175 17. 80+ PER 3.... MIK MEK-.. 0.5 175 17 .08 PER MIK/MEK-.. 0.5 175 17 .08 PER 4.-.. MIK/MEK--. 1.0 175 17 41 PER 3...- MIK/MEK... 0.5 175 .5 2 PER 4... 2 MIK/MEK--. 0.5 175 17 .08 PER 2...- 124 MIK/MEK..- 0.5 175 17 2 PER 5...- 52 MEK/Diox... 0.5 175 17-- .25 PER 5.-.- 52 MIK/MEK.-. 0.5 175 17 75 PER 2...- 99 MIK/MEK--. 0.5 175 17-- 32 PER 4 96 %g]1IEI%%EK..- 0.5 175 2 .08 10x.-- PER 5-... 0.5 80+ }PER 3.... 2s MEK/MIK--- 0.5 175 17+ 2 1 MEK is abbreviation for methyl ethyl ketone.

Z MIK is abbreviation for methyl isobutyl ketone.

3 All acid condensates dissolved in 50% MEK.

4 DMSO is abbreviation for Dimethyl Sulfoxide.

5 Except as noted in footnote 6, this amount of condensate was fused with the active compound on a 1:1 equivalent Weight basis and dissolved in methyl ethyl ketone to e. non-volatile content of 50% before use.

0 This amount of condensate was fused with the active compound on a 1:1 equivalent weight basis and dissolved in dioxanc to a non-volatile con tent of 50%beforeuse.

In order to demonstrate preparation of foam resin structures in accordance with the invention, the following examples were prepared:

Example CXXXI.--268 parts of the acid condensate AC 1 and 1220 parts of the active compound PER 1 were heated to obtain a molten mixture, after which 74 parts of polyoxyethylene sorbitan mono-oleate, an emulsifier sold under the trade-name Tween 80 by Atlas Powder Company, and 3.6 parts of triethylarnine were added with stirring to form a homogeneous mixture. 906

which is the condensation product of (a) formaldehyde creased to 421 parts, the amount of PER 1 was decreased to 488 parts, the amount of emulsifier was decreased to 45 parts and the triethylamine was omitted entirely. The result foam was similar to that of Example CXDQCI except that it displayed a tendency toward brittleness.

Example CXXXIV.Example CXXXI was repeated except that the amount of isocyanate was decreased to 544 parts, the amount of emulsifier decreased to 60 parts and 921 parts of the polyester active hydrogen compound PER 3 was substituted for that of Example CXXXI. Very little difference in the product was noticed as it was still an'irregular yellow foam that was rigid, hard and tough. 7

Example CXXXV. -Example CXXXIV was repeated except that the amount of the acid condensate was increased to 788 parts, the amount of the isocyanate to 1431 parts, the amount of the emulsifier to 76 parts while the amount of PER 3 was decreased to 743 parts. The product was substantially similar to that resulting in Example CXXXIV except for a tendency toward brittleness.

Example CXXXVI. Example CXXXI was repeated except that 620 parts of the acid condensate AC 4 were substituted, the amount of PER 1 decreased to 930 parts and the amount of emulsifier increased slightly to 78 parts. These changes did not cause a significant change in the properties of the foam other than adding a slight tendency toward brittleness.

Example CXXXVlL-Example CXXXI was repeated except for the omission of the tn'ethylamine. The prodnet was not observably different from that of Example j' CXXXI. a

The aforegoing examples, both as to films and foams, are furnished only for the guidance of those seeking to practice the invention and not for the purpose of defining V,

the boundaries in which it is operative. The numerous other embodiments are possible and will be suggested by For action to an intermediate stage and effect the final cure by exposure either to room temperature for a long period of time or to a further heat treatment. .It will also be understood that although the examples in the tables were converted to the insoluble, infusible state by means of heat, this was done largely in the interest of saving time and the same result can ordinarily be obtained at room temperature for much longer periods of time.

It is contemplated by the invention that various inactive ingredients, such as fillers, pigments and plasticizers can be added to the reaction mixture to modify the product in known ways. For example, the admixture of a pigment would be suggested where the product was to be used as a decorative coating as a replacement for paint. Inert fillers, such as siliceous and metallic powders might be added Where the specific application demands a product having unusual structural strength or resistance to heat.

It is claimed and desired to secure by Letters Patent:

1.. A composition of mat ter comprising the reaction product of (A) an organic polyisocyanate, (B) anorganic compound containing at least two active hydrogen atoms, each of said active hydrogen atoms being present in a compound selected from the group consisting of polyesters which are the reaction products of polyhydric alcohols and polycarboxylic acids, polyhydric alcohols, polyhydric phenols, polyamines, polyamides, polycarboxylic acids, mixtures thereof and any of the above'compounds in which at least one oxygen atom has been replaced by sulfur and (C) a resinous polycarboxylic acid 'and (b) a pentanoic acid consisting essentially of 4,4 bis(4-hydroxyaryl)pentanoic acid wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of from 1-5 carbon atoms, with saidhydroxyphenyl radical having hydrogen on at least one position ortho to the hydroxyl, wherein the ratio of (a) to (b) is from 1-4 moles of (a) per mole of (b); wherein (A) and (B)+(C) are present on an equivalent ratio of from about 5 :1 to 1:5 with (B) constituting from 565% of (EH-(C).

2. The compositionof matter of claim 1 where the pentanoic acid of (Cb) consists es's'eritially'of 4,4 bis(4- hydroxyaryl)pentanoic acid wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of one carbon atom.

3. The composition of matter of claim 1 wherein the pentanoic acid of (Cb) is 4,4 bis(4-hydroxyphenyl) pentanoic acid. .f

4. The composition of matter of claim 3 wherein (A) and (B) +(C) are present on an equivalent ratio or from about 2:1 to 1:2 with (B) constituting from 565% of 5. The composition of matter as described in claim 4 wherein (A) is an aromatic polyisocyanate.

6. The composition of matter as described in claim 4 I wherein (A) is an aliphatic polyisocyanate.

7. The composition of matter comprising the reaction product of (A) a mixture of organic monoisocyanates and polyisocyanates wherein at least of the mixture is a polyisocyanate, (B) an organic compound containing at least two active hydrogen atoms, each of said active hydrogen atoms being present in a compound selected from the group consisting of polyesters which are the reaction products of polyhydric alcohols and polycarboxylic acids, polyhydric alcohols, polyhydric phenols, polyamines, polyamides, polycarboxylic acids, mixtures thereof and any of the above compounds in which at least one oxygen atom has been replaced by sulfur and (C) a resinous polycarboxylic acid which is the condensation product of (a) formaldehyde and (b) a pentanoic acid consisting essentially of 4,4 bis(4-hydroxyaryl)pentanoic acid wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of from 1-5 carbon atoms with said hydroxyphenyl radical having hydrogen on at least one position ortho to the hydroxyl, wherein the ratio of (a) to (b) is from 1-4 moles of (a) per mole of (b); wherein (A) and (B)+(C) are present on an equivalent ratio of from about 5:1 to 1:5 with (B) constituting from 5- of (B)-|-(C).

8. A composition of matter comprising the cellular reaction product of (A) an organic polyisocyanate,v (B) an organic compound containing at least two active hydrogen atoms, each of said active hydrogen atoms being present in a compound selected from the group consisting of polyesters which are the reaction products of polyhydric alcohols and polycarboxylic acids, polyhydric alcohols, polyhydric phenols, polyamines, polyamides, polycarboxylic acids, mixtures thereof and any of the above compounds in which at least one oxygen atom has been replaced by sulfur, (C) a resinous polycarboxylic acid which is the condensation product of (a) formaldehyde and (b) a pentanoic acid consisting essentially of 4,4 bis(4-hydroxyaryl)pentanoic acid wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of from 15 carbon atoms with said hydroxyphenyl radical having hydrogen on at least one position ortho to the hydroxyl, wherein the ratio of (a) to (b) is from 1-4 moles of (a)per mole of (b); wherein (A) and (BM-(C) are present on an equivalent ratio of from about 5:1 to 1:5 with (B) constituting from 5 65% of (B)'-|'-(C), and (D) up to about 5% of (A), (B) and (C) of water.

9, A method of preparing a new composition of rnatcit ter which comprises admixing (A) an organic polyisocyanate, (B) an organic compound containing at least two active hydrogen atoms, each of said active hydrogen atoms being present in a compound selected from the group consisting of polyesters which are the reaction products of polyhydric alcohols and polycarboxylic acids, polyhydric alcohols, polyhydric phenols, polyamines, polyamides, polycarboxylic acids, mixtures thereof and any of the above compounds in Which at least one oxygen atom has been replaced by sulfur and (C) a resinous polycarboxylic acid which is (the condensation product of (a) formaldehyde and (b) a pentanoic acid consisting essentially of 4,4 bis(4-hydroxyaryl)pentanoic acid Wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of from 1-5 carbon atoms with said hydroxyphenyl radical having hydrogen on at least one position ortho to the hydroxyl, wherein the ratio of (a) to (b) is from 1-4 moles of (a) per mole of (b); wherein (A) and (B)+ (C) are present on an equivalent ratio of from about 5:1 to 1:5 with (B) constituting from 565% of (B)+(C), and heat converting said mixture to an insoluble, infusible resin.

References Cited in the file of this patent Bader et al.: Journal ofAmerican Chemical Society, volume 76, pages 4465-4466.

Patent No. 2,907 719 UNITED STATES-PATENT OFFICE CERTIFICATE'OF CORRECTION October o, 1959 Sylvan O. Greenlee' It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, line 5, for diphenolic acids" read Diphenolic Acid column 5, line 13, for "ad" read and column 5, line 31, for "diphenolic acids" read Diphenolic Acid ----g column 11, Table I, second column thereof, first line-of Example No. l, for "diphenolic acid" read Diphenolic Acidsame column 11, Table I, second column thereof, last line of Example No. 2, for "amount" read amounted "3 same column 11, Table I, second column thereof, first line of Example No. :3, for "DA?" read DPA column 12, Table I, second column thereof, first lines of Examples No. 5 and 6, for "diphenolicacid", each occurrence, read Diphenolic Acid ----5 same column 12, Table I second column thereof, line 10 of Example N0. 6, for "the" read the columns 13 and 14,

Table II, first column thereof, first line, for "E. l, du Pont de Nemours 82 Co. Incri read E, I. du Pont de Nemours 81 C0 Inc. Hylene T; Hy T same columns 13 and 14, Table II, first column thereof, last line, for "Durenedissocyanate" read Durenedgigisocyanate columns 21 and 22, Tgble IV-D, heading to second: column thereof, for Acid condensate read Acid 5? condensate same columns 21 and 22, footnote 3 of Table IV should appear as ,shown below instead of as in the patent:

All acid condensates dissolved in 50% MEK in Examples XLV-LXXII.

column 24, line 21, for "or from".read of from Signed and sealed this 8th day of November 1960 (SEAL) Attest:

KARL H. AXLINE ROBERT C, WATSON Attesting Officer Commissioner of Patents 

1.
 8. A COMPOSITION OF MATTER COMPRISING THE CELLULAR REACTION PRODUCT OF (A) AN ORGANIC POLYISOCYANATE, (B) AN ORGANIC COMPOUND CONTAINING AT LEAST TWO ACTIVE HYDROGEN ATOMS, EACH OF SAID ACTIVE HYDROGEN ATOMS BEING PRESENT IN A COMPOUND SELECTED FROM THE GROUP CONSISTING OF POLYESTERS WHICH ARE THE RACTION PRODUCTS OF POLYTHDRIC ALCOHOLS AND POLYCARBOXYLIC ACIDS, POLYHYDRIC ALCOHOLS, POLYHDRIC PHENOLS, POLYAMINES, POLYAMIDES, POLYCARBOXYLIC ACIDS, MIXTURES, THEREOF AND ANY OF THE ABOVE COMPOUNDS IN WHICH AT LEAST ONE OXYGEN ATOM HAS BEEN REPLACED BY SULFUR, (C) A RESINOUS POLYCARBOXYLIC ACID WHICH IS THE CONDENSATION PRODUCT OF (A) FORMALDEHYDE AND (B) A PENTANOIC ACID CONSISTING ESSENTIALLY OF 4,4 BIS(4-HYDROXYARYL)PENTANOIC ACID WHEREIN THE HYDROXYARYL RADICAL IS A HYDROXYPHENYL RADICAL AND IS FREE FROM SUBSTITUENTS OTHER THAN ALKYL GROUPS OF FROM 1-5 CARBON ATOMS WITH SAID HYDROXYPHENYL RADICAL HAVING HYDROGEN ON AT LEAST ONE POSITION ORTHO TO THE HYDROXYL, WHEREIN THE RATIO OF (A) TO (B) IS FROM 1-4 MOLES OF (A) PER MOL OF (B); WHEREIN (A) AND (B) + (C) ARE PRESENT ON AN EQUIVALENT RATIO OF FROM ABOUAT 5:1 TO 1:5 WITH (B) CONSITUTING FROM 5-65% OF (B) + (C), AND (D) UP TO ABOUT 5% OF (A), (B) AND (C) OF WATER. 